DE2627878C2 - Negative type silver halide photographic light-sensitive recording material and photographic developing solution therefor - Google Patents

Description

no

I IVJ

contains, in which at least one radical R is a piperidyl, pyrrolidyl, pyrryl or thioaryl group, two R radicals together can complete a benzodioxaring and any other ReUe R alkyl, Mean alkoxy, aryl, aryloxy or aralkyl groups.

5. Developer solution according to claim 4, characterized in that it is dipyrryl-1-phenylphosphine as the phosphine compound, Diphenyl-1-pyrrylphosphine, Diphenoxy-1-pyrrolidylphosphfn, diethoxy-1-pyrrylphosphine, Dipyrrolidyl-1-phenylphosphine, diphenyl-1-pyrrolidylphosphine and / or diphenyl-1-thiophenylphosphine contains.

6. Developer solution according to claim 4 and 5, characterized in that it contains the phosphine compound a concentration of 0.01 to 0.3 g per liter.

The invention relates to a light-sensitive photographic recording material containing silver halide negative type containing a phosphine compound and a photographic developing solution for a photosensitive one photographic containing silver halide ^. Negative type recording material having a Phosphine compound in the developer solution. Among a photosensitive photographic silver halide containing Recording material of the negative type is to be understood as a recording material in which by Exposure generates a latent image and this is made visible as a negative image by chemical development will.

From US-PS 36 81 078 and 37 17 466 certain selenium compounds are used as sensitizers or antifoggants known.

These are selenium compounds with quaternary phosphine groups bonded to the central selenium atom. With these selenium compounds, too, it is a disadvantage that they are always only very unpleasant experimental conditions can be produced.

The invention is therefore based on the object of improving the gradient in negative-working photographic recording materials without impairing other photographic properties It is relatively easy to use connections that can be established.

The object is achieved in that the recording material! and / or the developer solution as a phosphine compound one of the general formula

PR,

contain, in which at least one radical R door is a piperidyl, pyrrolidyl, pyrryl or thioaryl group, two

R radicals together can complete a benzodioxaring and any other radicals R are alkyl, alkoxy, Mean aryl, aryloxy or aralkyl groups. | The way in which the phosphine compounds are added to the emulsions is not critical and can be used during

any stage of manufacture, d. H. during the precipitation of the silver halides, the ripening, the redispersion after washing to remove water-soluble alkali or ammonium salts, digestion or as a final addition immediately before coating. The connections can also in a layer that is adjacent to the emulsion layer. The silver halide emulsion layer can be spectrally sensitized or not be sensitized. The optimal amount to be added for each emulsion can be determined by a simple experiment can be determined, as is customary in the production of emulsions. Preferably cherishes the Concentration between 0.005 and 0.5 g / 1.5 mol of silver halide in the emulsion. Particularly preferred Phosphine compounds with thiophenyl substituents. Representative phosphine compounds are below Named:

Connection designation

No.

formula

Dipyrryl-1-phenylphosphine Diphenyl-1-pyrrylphosphiii Diphenoxy-1-pyrrolidylphosphine

V-O-

O-P

C ₂ H ₅

ι ⁴

Diethoxy-1-pyrryphosphine Dipyrrolidyl-1-phenylphosphine

H ₅ C ₂ -OP

Diphenyl-1-pyffölidylphosphine

f Vp

continuation

Connection designation

No.

formula

2 (l-piperidyl) -2-benzodioxa-1,3-phosphine

Diphenyl-1-thiophenylphosphine

The phosphine compounds according to the invention can be used in the developer solutions in amounts of 0.0005 up to 1.0 g / l can be used. An amount in the range from 0.01 to 0.3 g / l is particularly preferred. The developer solutions contain known developer substances, e.g. B. Hydroquinone and its derivatives, such as Methylhydroquinone, catechol and pyrogallol. In general, a pH above 8 is used.

The phosphine compounds according to the invention also include mixtures of different phosphine compounds.

The photosensitive silver halide emulsions can be mixed with noble metal salts and compounds with labile sulfur atoms, e.g. B. gold chloride and sodium thiosulphate, chemically sensitized. Further Additives, e.g. B. hardeners, wetting agents and plasticizers can be added in the usual way. As antifoggants or stabilizers, for. B. Azaindolizine (Tetraazaindenes) can be used.

As a silver halide z. B. silver chloride and silver bromide, but also silver bromide chloride and silver bromide iodide in question. Particularly good results are obtained with recording materials of the lith type, which contain silver bromide chloride. Gelatin is the preferred binder, but it can partially carry through synthetic binders are replaced. For example, binders that are also used to increase the Opacity are suitable e.g. B. dextran, dextrin and polyvinylpyrrolidone, and latices of polymers such as polyethyl acrylate, which are valuable for improving dimensional stability are advantageously incorporated into many kinds of silver halide emulsions used for the purpose of the invention. The latices of polymers are particularly advantageous in lith-type recording materials such as in US Pat. No. 3,142,568 and US Pat 33 05 286 written.

The invention is further elucidated by the following examples.

example 1

On a conventionally produced lith-type recording material with a silver halide emulsion layer, which contained 30 mol% silver bi'omide and 70 mol% silver chloride, became a stepped gray wedge with vT levels plus 100-line grid with square dots copied onto 32 seconds meter candles. rehearse of these were for 2 minutes at 27 ° C in a ^ m commercial, high-contrast hydroquinone-formaldehyde-bisulfite developer developed.

The following phosphine compounds were added to different parts of the developing solution, are marked with the same numbers as in the table above, in the specified quantities added.

⁵⁵ Table I

Compound and amount / liter of developer solution

D _m , "

Relative gradient

Sensitivity (density = (density = 3.5) 0.3 to 3.5)

Comparison test without addition of 0.281 g compound? 0.590 g compound 5 0.0118 g compound 5 0.287 g compound 3 0.287 g compound 4

0.03 5.8 100 7.33 0.03 5.8 100 8.93 0.03 5.8 50 17.3 0.03 5.8 100 10.4 0.04 5.8 122 7.9 0.04 5.8 92 8.3

The values show that the gradient can be improved with phosphine compounds according to the invention, without changing other properties significantly / u. However, the sensitivity can be impaired if too much is used.

B e i s ρ i e I 2

To an acidified solution of gelatin which contained 1.5 mol of KCl and 0.3 g of the compound PhcnyIdiphenylthiophosphinit, 1.5 mol of silver nitrul in aqueous solution were quickly added. After adding 0.6 mol of KBr aqueous solution, the mixture was allowed to ripen for 10 minutes, after which 0.9 mol of KBr aqueous solution was added and the mixture was allowed to ripen for 10 minutes. All measures were carried out at 71 ° C. The E. emulsion obtained was cooled, coagulated, washed and redispersed as described in US Pat. No. 2,772,162. The emulsion was divided into two parts. I in part served as a comparative sample, and in the other part 0.3 g of the above-mentioned compound 8 was added per 1.5 moles of silver halide. In addition, the emulsion was sensitized with the usual gold and sulfur compounds and left to digest at 52 ° C. for 60 minutes, when the negative emulsion was obtained. N.ich coating and drying a stepped gray wedge having Vt levels was aufkopiert to actinic radiation corresponding to 4470 seconds meter candles, followed by 2 minutes developed at 2O ⁰ C in a conventional N-methyl-p-aminophenol sulfate-hydroquinone developer and fixed, washed and was dried. The sensitometric data obtained are given in the table below.

Table II

Sample no.

D = n, 3 to OM
Factor value i-'actor

additive gradient D = 0.2 to 0.66 Whom Control without addition 0.183 0.3 g V ^r bond 8 0.26

ix 0.151 ix

1.42X 0.41 2.61X

The gradient was improved regardless of the density range used for the calculation if the Connection 8 was present.

Example 3

A silver halide emulsion was prepared in the manner described in Example 2
decided that no phosphine compounds were added to the aqueous gelatin salt solutions. After the precipitation, the emulsion was washed and redispersed. After the redispersion, the remaining gelatin was added and the temperature increased to 54 ° C. At this point the emulsion was divided into five parts of 4C. One part served as a comparative sample. The various phosphine compounds listed in the table below were added to the other four parts in the amounts indicated. The emulsions were then ripened for 60 minutes. They were applied to the carrier, dried and cut into sensitometer strips, which were exposed and processed in the manner described in Example 2. The results are given in the table below. The specimens were exposed and tested in the fresh state and after aging in the oven.

Table III

Sample No. Addition per 1.5 mol of silver halide test age £>"," D _max 5C

fresh
oven

fresh 0.03 2.30 ₅ <

oven

fresh
oven

fresh oven

fresh oven

The results show that the phosphine compounds are also effective as antifoggants. The compounds generally cause an increase in B _max upon oven aging and not a decrease as is common with some known antifoggants. Similar results were obtained when the phosphine compound 2 was added as a final additive.

1 without 2 0.1 g compound 2 3 0.2 g compound 4 4th 0.1 g compound 6 5 0.1 g of compound 8

0.12 2.52 0.95 1.90 0.03 2.30 0.15 2.59 0.04 2.16 0.12 2.59 0.03 1.35 0.32 2.68 0.03 1.75 0.09 2.71

Example 4

The experiment described in Example 3 was repeated with the difference that enough portions of the Emulsion were used to make a set whose emulsions had been post-ripened for 60 minutes, and s to form another set whose emulsions were ripened for 120 minutes at 52 ° C. After this time the compounds mentioned in the table below were added and the emulsions in the above described manner applied to the carrier. The results of the measurements in the sensitometer are as follows Called table.

10 Table IV

Sample no.

In addition per 1.5 moles of silver halide

Prüfaller

Sensitivity (density = 1.5)

Maturing time 60 minutes

1 without

2 0, i g connection S.

3 0.1 g compound 2

Maturing time 120 minutes

1 0.1 g compound 8

2 0.1 g compound 2

The anti-fogging effect is noticeable even with long digestion times.

Example 5

An emulsion was prepared in the manner described in Example 2 with the difference that sufficient Sulfur compound was added as a sensitizer to raise the fog intensity to higher than normal and to illustrate that the added phosphine compound reduces this variance. the Results of the measurements in the sensitometer are given in the following table, in which the amount of sulfur sensitizer is expressed relative to the amount in the emulsions of Example 2.

Table V

fresh
oven 0.04
0.09 2.05
2.39 100
85 Ii iSCif
oven η m
o! o3 1 TC
U2 25th
25th fresh
oven 0.02
0.08 1.92
1.81 62
41 fresh
Oren 0.03
0.02 1.97
2.08 49
49 fresh
oven 0.04
0.05 2.67
2.51 97
77

Sample No. Additions per 1.5 moles of silver halide relative amount of phosphine compound

Test age

without

0.2 g compound 2

without

0.2 g compound 2

·) Aged at room temperature.

1 IX 50 2 IX 3 2x "4 2x

fresh 0.04 2.00 3 months·) 0.14 2.58 fresh 0.04 1.98 3 months*) 0.14 2.10 fresh 0.46 2.07 3 months*) 0.74 1.48 fresh 0.15 2.18 3 months*) 0.30 1.89

The results show that the phosphine compounds exist in a high concentration in the presence of one Sulfur sensitizer is able to reduce the veil intensity considerably.

Example 6

A silver halide emulsion was prepared in the manner described in Example 2 with the difference that that instead of 0.3 g of compound 8 per 1.5 mol of silver halide, smaller amounts of compound 8, which are then mentioned in the table below, were added.

Tabel VI veil i months oven fresh 3 months oven sample additive fresh 0.05 0.24 0.80 1.18 2.37 No. 0.04 0.04 0.04 0.48 0.62 2.08 1 without comparison sample 0.03 0.04 0.04 O, 4Y 0, b ' 2.50 2 0.1 g of compound 8 0.03 0.04 0.04 0.70 1.04 2.62 3 0.05 g Vt. binding 8 0.03 0.04 0.08 0.91 1.24 2.49 4th 0.025 g of compound Ii 0.03 0.04 0.05 0.81 1.14 2.62 5 0.01 g of compound 8 0.03 6th 0.005 g of compound 8

Claims (4)

Patent claims: 1. Negative type silver halide photographic light-sensitive material with a phosphine compound, characterized in that it is a phosphine compound at least one of the general formula PR ₃ contains, in which at least one radical R is a piperidyl, pyrrolidyl, pyrryl or thioaryl group, two R radicals together can complete a benzodioxaring and any other radicals R alkyl, Mean alkoxy, aryl, aryloxy or aralkyl groups. 2. Recording material according to claim 1, characterized in that it is used as a phosphine compound Dipyrryl-l-phenylphosphi ^ Diphenyl-l-pyrrylphosphine.Diphenoxy-l-pyrrolidylphosphine.Diäthoxy-l-pyrrylphosphine, Dipyrrolidyl-1-phenylphosphine, diphenyl-1-pyrrolidylphosphine and / or diphenyl-1-thiophenylphosphine contains. 3. Recording material according to spoke 1 and 2, characterized in that it is the phosphine compound at a concentration of 0.005 to 0.5 g per 1.5 moles of silver halide. 4. Photographic developer solution for a light-sensitive photographic silver halide-containing product Negative type recording material having a phosphine compound in the developing solution, then characterized in that they contain at least one of the general formula as the phosphine compound